Reaction product of aldehydes and diazine derivatives



isopropylphenyi,

Patented Mar. 2, 1943 i Y STATES nmo'rron rnonno'r o'r at 1 1) name Gaetano F. DAielio, Pld, or to General Electric Company, a corporation oi New York no Drawing. Application January 30, Serial No. 428,906

20 Claims.-

formula In. the above formula 11. represents an integer 2 and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, Y represents a.divaient carbocyclic radical, and R. represents a member of the class consisting of hydrogen and monovalent hydrocarbon and substituted hydrocarbon radicals, more particularly halohydrocarbon radicals. Since 11. represents an integer which is l or 2, it will be seen that the linkage of the carbocycliccarbamyl-alkyl grouping to the sulfur atom in all cases will be alpha or beta to the carbocycliccarbamyl or -thiocarbamyl grouping. It also will be observed that linkage of the diazinyi grouping to the sulfur atom is through a carbon atom.

Illustrative examples of radicals thatR in the above formula may represent are: aliphatic. (e. g... i

methyl, ethyl, propyl, isopropyl, aliyl, butyl, secondary butyl, isobutyl, butenyl, amyl, isoamy hexyl, heptyl, octyl, nonyi, etc.) including cyclealiphatic (e. g., cyclopentyl. cyclopentenyl; cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, etc.); aryl (e. g., phenyl, diphenyl or xenyl,

amyl. chlorophenyl, bromophenyl, iodophenyl, fluorophenyl; dichlorophenyl, trichlorophenyl, chloronaphthyl, dibromophenyl, tribromophenyl, chlorotolyl, iodotolyl, diohlorotolyl, bromotolyl,

dibromotolyl, fiuorotolyL' chlorocyclohexyl, chlorocyclohexenyl, ethyl chlorophenyl, ethyl 'bromophenyl, propyl chlcrophenyl, phenyl derivative corresponding to the following general naphthyl, anthracyl, etc.); aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, allylphenyl, z-butenylphenyl, tertiary-butylphenyl, isoamy lphenyl, etc.); arylsubstituted aliphatic (e. 3:, benzyl, phenviethyl, phenylpropyl, phenylisopropyl, phenylamyl, cinnamyl, etc.); and their homologues, as well as those groups with one or more of'theirhydrogen atoms substituted by, for example. a halogen, specifically chlorine, fluorine, bromine or iodine. Specific examples of halogenosubstituted hydrocarbon radicals are chloromethyl, chloroethyi,

- bromomethyl, bromoethyi, chloropropyl, bromopropyl, iodopropyl, iodoamyl, chioroamyl, bromochloroethyl, chlorohexyl, etc. Preferably R in the general formulas and, more particularly,

where n, *Z, Y and R have the same meanings as above given with reierence'to Formula I.

Illustrative examples oi-divalent carbocyclic radicals-that Y in Formulas I, II and 111 may represent are: divalent aryl, er 8., phenylene, xenylene, naphthyiene, etc.; divalent aliphaticaryl, e. g.-, 2,5-toluylene, 1,4-dimethyi 2,3-phenylene, .etc.; divalent cycloaliphatic, e. g., cyclopentylene, cyclohexylene, cyclopentenylene, cy-p 'clohexenylene, cycloheptylene, etc.; and their homologues, as well as those divalent carbocyclic, radicals with one or more of their hydrogen atoms replaced by a substituent, e. g., halogeno,

amino, acetyl, hydroxy, acetow, alkoxy, aryloxy, v

sulfamyl, aikyl, alkenyl, a C0ORJ group or groups in addition to the single -COOR. group shown in the above gormulas, etc. Specific examples of substituted divalent carbocyclic radicals are chlorophe'nylehe, bromophenylene, chloronaphthylene, bromonaphthylene, bromo 2,5-toluylene, chlorocyclopentylene, chlorocyclopentenylene, hydroxyphenylene, 'ethoxyphenyl- .ene, acetophenylene, acetoxyphenylene, bromospending 1,2- or ortho-diazines (pyridazines) or the 1,4- or para-diazines (pyrazlnes) may be used. Also, instead of the diazinyl monosulfides represented by the above formulas, the dland tri-sulfides of the diazines (ortho, meta or para) may be employed.

The diaz'ine derivatives that are used in carrying the present invention into effect are more fully described and are specifically claimed in my copending application Serial No. 428,905, filed concurrently herewith and assigned to the same assignee as the present invention. As pointed out in this copending application, a. suitable method of preparing the diazine derivatives employed in practicing the present invention comprises efiecting reaction between a diamino [(-NHR) 2] mercapto pyrimidine and a carboxy-. carboaliphaticoxy-(including carbocycloaliphativcoxy-) or carboaromaticoxy carbocyclic-carbamyl or -thiocarbamyl-alkyl halide in the presence of a hydrohalide acceptor, e.vg., an alkalimetal hydroxide. When a carboxy(--COOH)- carbocyclic-carliaxnyl or -thiocarbamyl-alkyl halide is used as a starting reactant and the proportions of reactants and reaction conditions are such that the hydrogen atom of the COI-I group of the carboxy-carbocyclic compound is replaced by the residue of the hydrohalide acceptor, e. g., by an alkali metal, the carboxy compound desired as a, final product is obtained by treating this intermediate product with hydrochloric, hydrobromic, sulfuric or other suitable inorganic or organic acid in an amount just sufficient to form the desired carboxy derivative.

Specific examples of diazinyl carbocyclic-carbamyl-alkyl sulfides and diazinyl carbocyclicthiocarbamyl-alkyl sulfides that may be used in producing my new condensation products are listed below:

The diamino pyrimidyl ortho-, metaand para-, carboxy-, carboalkoxyand carboaryloxyphenyl-carbamyl-methyl sulfides The diamino pyrimldyl orthoe; metaand para-,

carboxy-, carboalkoxyand carboaryloxyphenyl-thiocarbamyl-methyl sulfides The diamino pyrimidyl ortho-, metaand para-,

carboxy-, carboalkoxyand carboaryloxy-tolylcarbamyl-methyl sulfides The diamino pyrimidyl ortho-, metaand para-, carboxy-g carboalkoxyand carboaryloxy-tolyL- thiocarbamyl-methyl sulfides The di-(methylamino) pyrimidyl ortho-, metaand para-, carboxy-, carboalkoxy-' and carboaryloxy-phenyl-carbamyl-methyl sulfides The di-(ethylamino) fiyrimidyl ortho-, metaand para-, carboxy-, carboalkoxyand'carboaryloxy-phenyl-thiocarbamyl-methyl sulfides The di-(anilino) pyrimidyl ortho-, metaand para-, carboxy-, carboalkoxyand carboaryl- 6(')' fide oxy-tolyl-carbamyl-methyl sulfides The di-(cyclohexylamino) pyrimidyl ortho-f metaand para-, carboxy-, carboaryloxyand carboalkoxy tolyl-thiocarbamyl-methyl sulfides The diamino pyrimidyl -alpha-(ortho-, metaand -para-, carboxy-, carboalkoxyand carboaryloxy-phenyl carbamyl-ethyl) sulfides -'Ihe diamino pyrimidyl beta-(ortho-, metaand para-, carboxy-, carboalkoxyand carboaryls'oxy-phenyl-carbamyl-ethyl) sulfides The diamino pyrimidyl alpha-(ortho-, metaand para-fcarboxr, carboalkoxy and carbonyloxy-phenyl-tluocarbamyI-ethyl) sulfides The diamino pyrimidyl beta-(ortho-, metaand para-, carboxy-, carboalkoxyand carboaryh oxy-phenyl-thiocarbamyl-ethyl) sulfides The diamino pyrimidyl ortho-, metaand para-,

.carbohaloalkoxyand carbohaloaryloxyphenyl-carbamyl-methyl sulfides The diamino pyrimidyl ortho-, metaand para-,

carbocycloallphaticoxyand carbohalocycloaliphaticoky-phenyl-carbamyl-methyl sulfides 10 The diamino pyrimidyl ortho-, metaand para-,

carboalkenyloiqrand carbohaloalkenyloxytolyl-carbamyl-methyl sulfides The diaminomyrimidyl 0rtho-, metaand para-,

carbocycloalkenyloxyand carbohalocycloalkenyloxy-phenyl-carbamyl-methy1 sulfides The diamino pyrimidyl alpha-(ortho-, metaand para-, carboxy-, carboalkoxyand carboaryloxy-tolyl-carbamyl-ethyl) sulfides The diamino pyrimidyl beta-(ortho-, metaand para-, carboxy-, carboalkoxyand carboaryloxy-tolyl-carbamyl-ethyl) sulfides The diamino pyrimidyl alpha-=(ortho-, metaand para-, carboxy-, carboalkoxyand carboaryloxy-tolyl-thiocarbamyl-ethyl) sulfides The diamino pyrlmidyl beta-(ortho-, metaand para carboxy-, carboalkoxyand carboaryloxy-tolyl-thiocarbamyl-ethyl) sulfides The 4,6-di-(methylamino) fi-alkyl (e. g., methyl.

ethyl, etc.) pyrimidyl-2 alpha-(ortho-, metaand para-, carboxy-, carboalkoxyand carboaryloxy-phenyl-carbamyl-ethyl) sulfides The 2,6-di-(propylamino) 5-aryl (e. g., phenyl,

naphthyl, etc.) pyrimidyl-4 beta- (ortho-, metaand para-, carboxy-, carboalkoxyand carbo- 4,6-diamino pyrimidyl-2 carbobi'omophenoxyphenyl-carbamyl-methyl sulfide 2,6-diamino 5-benzyl pyrimidyl-4 'carbochloroethoxyphenyl-carbamyl-methyl sulfide 4,6-diamino 5-xenyl pyrimidyl-2 carbomethoxv cycloheptenyl-carbamyl-methyl sulfide 4,6-diamino pyrimidyl 2 carbobromophenoxycyclohexyl-carbamyl-methyl sulfide 4,6-diamino 5-chlorotolyl pyrimidyl-Z alpha- (ortho-carbobutoxvtolyl carbamyl-ethyl) sul- 4-ethylamino 5-hepty1 fi-amino pyrimidyl-fi beta- (meta carboethoxyphenyl-carbamyl-pentyl) sulfide 2,6 diamino 5 iodophenyl pyrlmidyl-4 beta- (para. carboethoxytolyl-thiocarbamyl-ethyl) sulfide 2-chlorocyclopentylamino 5-chloronaphthyl 6- benzylamino pyriniidyl-2 ortho-carbobutoxyphenyl-(bromoethyl) -carbamyl-methyl sulfide d-amino fi-fiuorotoluido pyrimidvl-2 carbopentoxytolyl-carbamyl-methyl sulfide bomethoncyclopentyl carbamyl 9 76 methyl sulfide 4-bromotoluido 6-benzylamino pyrimid'yl-2' car-- 4,6-diamino -methyl pyrimidyl-2 para-car xyphenyl-carbamyl-methyl sulfide 4 chlorobenzylamino 5-chlorobutyl G-bromoethylamino pyrimidyl-2 beta- [carboxyxenyl- (butylphenyll-carb'amyl (alpha-naphthyD- ethyl] sulfide V 4,6-diamino fi-bromotolyl pyrimidyl-2 beta- [4'- carboethoxy 2'-chloro cyclopentyl-(xenylb carbamyl-(beta-chloroxylyl)-ethyll sulfide Additional examples of diazine derivatives that may be employed in producing the new condensation products of the present invention are given, in my above-identified copending application Serial No. 428,905.

The present invention is based on my discovery that new and valuable, materials of particular utility in the plastics and coating arts can be pronot entirely satisfactory for use in many applica.

tions, for instance in the production of molding compounds having a high plastic fiow durin molding combined with a rapid cure to an insoluble, infusible state. Surprisingly it was found that the heat-curable resinous condensation products of this invention and molding compositions made therefrom show excellent fiow characteristics during a short curing cycle. This is a property that is particularly desirable in a thermosetting resin and molding .compound. The

molded articles have a high dielectric stren th.

and excellent resistance to arcing. They have a good surface finish and excellent resistance to water, being better than the ordinary urea-formaldehyde resins in this respect. The cured resins have a high resistance to heat and abrasion, and therefore are especially suitable for use where optimum heatand abrasion-resistance are propcrties of primary importance,

In practicing my invention the initial condensation reaction may be carried out at normal or at elevated temperatures, at atmospheric, subatmospheric or super-atmospheric pressures,- and under neutral, alkaline or acid conditions. Preferably the. reaction between the components is initiated under alkaline conditions.

Any substance yielding an alkaline or an acid aqueous solution may be used in obtaining alkaline or acid conditions for the initial condensation reaction. For example, I may use an alkaline substance such as sodium, potassium or calcium hydroxides, sodium or potassium carbonates, mono-, diortri-amines, etc. In some cases it is desirable'to cause the initial condensation reaction between the components to take place in -the presence of a primarycondensation catalyst and a secondary condensation catalyst. The primary catalyst advantageously is either an aidehyde-non-reactable nitrogen-containing basic tertiary compound, e. g., tertiary amines such as trialkyl (e. g., trimethyi, triethyl, etc.) amines, triaryl (e. g., triphenyl, tritolyl, etc.) amines, etc., or an aldehyde-reactable nitrogen-containing basic compound, for instance ammonia, primary amines (e. g., ethyl amine, propyi amine, etc.)

and secondary amines (e. g., dipropyl amine, dibutyl amine, etc.)

less than the amount of the primary catalyst, advantageously is a fixed alkali, for instance a carbonate, cyanide or hydroxide of an alkali metal (e. g., sodium, potassium, lithium. etc.)

Illustrative examples of acid condensation cat-- alysts that may be employed are inorganic or organic acids such as hydrochloric, sulfuric, phosphoric, acetic, lactic, acrylic, malonic, etc., or acid salts such as sodium acid sulfate, monosodium phosphatemonosodium phthalate, etc. Mixtures of acids, of acid salts or of acids and of acid salts v may be employed if desired.

The reaction between the aldehyde, e. g., formaldehyde, and the diazine derivatives may be carried out in the presence of solvents or diluents, fillers, other natural or synthetic resinous bodies, or while admixed with other materials that also can react with the aldehydic reactant or with the j diazine derivative, e. g., ketones, urea (NI-hCONHz) thiourea, selenourea', iminourea (guanidine) substituted ureas, thioureas, selenoureas and iminoureas, numerous examples of which are given in various copending applications of mine, for instance in my copending application Serial No. 363,037, filed October 26, 1940; monoamides 0f monocarboxylic and polycarboxyiic acids and polyamides of polycarboxylicacids, e. g., acetamide, halogenated acetamides, (e. g., a chlorinated acetamide), maleic monoamide, malonic monoamide, itaoonic diamide, succinic diamide,

phthalic diamide, the monoamide, diamide and triamide of tricarballylic acid, etc.; aldehyde-reactable diazines other than'the diazine derivatives constituting the primary components of the resins of the present invention; aminotriazines, e. g., melamine, ammeline, ammelide,melem,melam, melon, numerous other examples being given in various copending applications of mine, for instance in application Serial No. 377,524, filed February 5, 194l,and in applications referred to in said copending application; phenol and substituted phenols, e. g., the cresols, the xylenols, the

- tertiary alkyl phenols and other phenols such as mentioned in my Patent 2,239,441; monohydric and polyhydric alcohols, e. g., butyl alcohol, ethyl alcohol, isoamyl alcohol, ethylene glycol, glycerine, polyvinyl alcohol, etc.; amines, including aromatic amines, e. g., aniline, etc.; and the like;

The modifying reactants may be incorporated with the diazlne derivative and the aldehyde by mixingall the reactants and efl'ecting condensation therebetween or by various permutations of reactants as described, for. example, in my copending application Serial No. 363,037 with particular reference to reactions involving a urea, an aldehyde and a semi-amide of oxalic acid. For instance, I may form a partial condensation product of ingredients comprising (1) urea-or 1 melamine or urea and melamine, (2) a diazine derivative of the kind described herein and in my copending application Serial No. 428,905, for example, a diamino pyrimidyl ortho-, metaor para-carboalkoxyphenyl (e. g., carboethoxyphenyl) or -carboaryloxyphenyl' (e. g., carhophenoxyphenyl) carbamyl-methyl sulfide, a diamino pyrimidyl ortho-, metaor para-carboal- 'koxytolyl-carbamyl-methyl sulfide, etc., and (3) an aldehyde, including polymeric aldehydes, hy-

- droxyaldehydes and aldehyde-addition products.

for instance formaldehyde, paraformaldehyde,

The secondary condensation catalyst, which ordinarily is used loan amount glyceraldehyde, dimethylol urea, a polymethylol melamine, e. g., hexamethylol melamine, etc. Thereafter I may effect reaction between this partial condensation product and, for example, a curing reactant, specifically a chlorinated acetamide, to obtain a heat-curable composition.

Some of the condenstion products of this invention are thermoplastic materials even at an advanced stage of condensation, while others are thermosetting or potentially thermosetting bodies that convert under heat or under heat and pressure to an insoluble, infusible state. The thermoplastic condensation products are of particular value as plasticizers for other synthetic resins. The thermosetting or potentially thermosetting resinous condensation products, alone or mixed with fillers, pigments, dyes, lubricants, plasticizers, curing agents, etc., may be used, for example, in the production of molding'compositions'.

Depending upon the particular conditions of reaction and the particular reactants employed, the intermediate or partial condensation products vary from clear, colorless or colored, syrupy, water-soluble liquids to viscous, milky, dispersions and gel-like masses of decreased solubility in ordinary solvents, e. g., ethyl alcohol, butyl alcohol, dioxane, Cellosolve, ethylene glycol, glycerine, etc. These liquid intermediate condensation products may be concentrated or diluted further by the removal or addition of volatile solvents to form liquid coating compositions of adjusted viscosity and concentrations. The heatconvertible or potentially heat-convertible resinous condensation products may be used in liquid state, for instance as surface-coating materials, in the production of paints, varnishes, lacquers, enamels, etc., for general-adhesive applications, in producing laminated articles and for numerous other purposes. The liquid heat-hardenable or potentially heat-hardenable condensation products also may be used directly as casting resins, while those which are or a gel-like nature in partially condensed state may be dried and granulated to form clear, unfilled heat-convertihie resins.

In order that those skilled in the art better may understand how thepresent invention may be carried into effect, thefollowing examples are Aqueous solution or sodium hydroxide (0.5

N) 2.0 Water 20.0 Chloroacetamide (monochloroacetamide) 0.3

Allot the above ingredients were mixed and were shaken intermittently at room tempera ture for one hour. The resulting reaction product was mixed with 24.1 parts alpha cellulose inflock form and 0.1 part of a mold lubricant, specifically zinc stearate. The resulting composition was dried at room temperature. A sample or the dried compound, when placed on a 140 C. hotplate, bodied to a resinous mass and slowly cured to an iniusible state. This example shows that reaction between the components can be efbe understood by those skilled in the art that the above ingredients also may be caused to react by heating at an elevated temperature, 'for' example at boiling temperature under reflux.

Aqueous solution of sodium hydroxide (0.5

N) 1.6 Water 20.0 Chloroacetamide 0.4

All of the above ingredients with the exception of the chloroacetamide were heated together 0 under reflux at the boiling temperature of the mass for 2 minutes. At the end of this period of time a resinous layer separated as a viscous, molasses-like syrup. The reaction product was mixed with 28.8 parts alpha cellulose, 0.1 part zinc stearate and the above-stated amount of chloroacetamide. The resulting wet molding composition was dried at room temperature until sufflcient moisture had been removed to provide a molding material that could be molded satisfactorily. A sample of the dried and ground molding compound was molded for 5 minutes at 140 C. under a pressure of 4,500 pounds per square inch. The molded disk was removed hot from. the molds It did not become distorted upon cooling to room temperature. The molded piece was well cured throughout and had a homogeneous and well-knit structure. It had very good resistance to water, as indicated by the fact that when it was immersed in boiling water for 15 minutes followed by immersion in cold water tor 5 minutes it absorbed only 1.4% by weight of water. The ordinary urea-formaldehyde resins yield molded articles which, when similarly tested, show a water-absorption value of about 5% to 7%. The molding compound of this example showed excellent plastic flow during molding.

Instead of using chloroacetamide in accelerating the curing of the potentially reactive resinous material, heat-convertible compositions may be produced by adding to the partial condensation product (in syrupy or other form) direct or aptive curing catalysts (e. g., citric acid, phthalic anhydride, malonic acid, oxalic acid, etc.), or latent curing catalysts (e. g., sodium chloroacetate,,,N-dieth'yl chloroacetamide, glycine ethyl ester hydrochloride, etc.), or by intercondensation with curing reactants other than monochloroacetamide (e. g., diand tri-chloroacetamides, chloroacetonitriles, alpha, beta-dibromopropionitrile, aminoacetamide hydrochloride, ethylene diamine monohydrochloride, the ethanolamine hydrochlorides, nitrourea, chloroacetyl urea, chloroacetone, glycine, sulfamic acid, diamide, phenacyl chloride, etc.); Other examples of active and latent curing catalysts and of curing reactants that may be employed to accelerate or to'eii'ect the curing of the therthis and other examples are given in various copending applications of'mine, for instance in copending applications Serial No. 346,962, filed July 23, 1940, andserial No. 354,395, filed August 27, 1940, both of which applications are assigned rooted at normal temperatures. 01 course it will to the same assignee as the present invention.

citric mosetting or potentially thermosetting resins of I Example 3 Parts 4,6-diamino pyrimidyl-2 para-carboethoxy- Aqueous solution of sodium hydroxide (0.5 N) 2.5 Chloroacetamide 0.3

All of the above components with the exception of the chloroacetamide were heated together under reflux at boiling temperature for 7 minutes. The resulting resinous syrup was mixed with 44.1 parts alpha cellulose, 0.2 part zinc stearate and the above-stated amount of chloroacetamide; The moding compound produced in this manner was dried at room temperature as described under Example 2. A sample of the dried and ground molding compound was molded for 5 minutes at 140 C. under a pressure of 4,000. pounds per square inch. The molded piece had a well-knit, homogeneous and well-cured structure. It had excellent resistance to water, as shown by the fact that it absorbed only 0.55% by weight of water when tested for its waterresistance characteristics as described under Example 2. The molding compound exhibited good plasticity during molding. 7

Example 4 ing temperature for 3 minutes. At the end of this period of time the aminotriazole was added and refluxing was continued for an additional 2 minutes. The chloroacetamide was now added and the resulting resinous syrup immediately was mixed with 25.1 parts alpha cellulose and 0.1- part zinc stearate. The resulting wet molding compound was dried at room temperature as described under Example 2. A sample of the dried and ground molding compound was molded into the form of a disk, using a. molding time of 5 minutes, a molding temperature of 140 C. and a molding pressureoi 4,500 pounds per square inch.- The molded disk was well knit and had a homogeneous and well-cured structure. The molding compound showed good plasticity during molding. The molded disk had good water resistance when tested for its water-resistance Aqueous ammonia (approx. 28% NHa) 1.0

characteristics as'described under Example 2.

' Example 6 Parts 4,6-diamino pyrimidyl-2 para-carboethoxyphenyl-carbamyl-methyl sulfide 17.4 Furfur 48.0

Aqueous solution of sodium hydroxide (0.5

were heated together under reflux at boiling tem- 30 perature for 15 minutes The resulting resinous syrup cured to a semi-infusible state when a small sample of it was heated on a- 140 C. hoting approx. 11% by weight of water) L--- 54.0

were heated together underreflux at boiling temperature for 3 minutes, at the end of which period'of time the reaction mass began to separate into 2 layers. The resinified mixture was 7 compounded with 52.3 parts alpha cellulose and 0.3 part zinc stearat'e. The wet compound was 7 dried atroom temperature as described under Example 2.. A well-cured molded piece having a well-knit and homogeneous structure was pro duced by molding a sample of the dried and ground molding rcompoundffor 5 minutes at -140 C. under a pressure of 5,600 pounds per.

Aqueous solution of vsodium hydroxide (0.5 N) I Chloroacetamide L- 0 .3

All of the above components with the exception of the 'aminotriazole and the chloroacetamide were heated together under reflux at boil- 75 positions.

Aqueous ammonia (approx; 28% NE) 3.5-

Aqueous solution of sodium 'hydroxide (0.5 N) 2.5 Water. 78.7 Chloroacetamide 0.4

v ration oi various coating materials and moldin plate. The addition of'chloroacetamide, glycine, phenacyl chloride and other curing agents such as mentioned under Example2 accelerated the conversion of the resin to a semi-infusible state when the'individual samples containing the curing agent were heated on a 140C. hotp late.

Upon further heating at this temperature the resin containing the curing agent cured slowly to a hard, infusible mass. The resin iilm formed in this .manner could be removed from the hotplate in sheet form. This sheet -material was extremely flexible and possessed excellent adhesive and cohesive characteristics. The resinous composition of this example may beused as a modifier of other synthetic resins or in the prepacompounds.

Example 7 I Parts 4,6 -diamino pyrimidyl-2 para-carboethoxy-.

phenyl-carbamyl-methyl sulfide 17.4 Butyl alcohol 37.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 40.5 Aqueous ammonia (approx. 28% NR1) 1.0

' Aqueous solution of sodium hydroxide (0.5

Example 5 3 Parts .4,6-diamino pyrimidyl-2 paraearboethoxy- I v phenyl-carbamyl-methyl sulflde 17.9 'Aminotriazole, specifically l-carbamyl guanazole 14.2 Aqueous formaldehyde (approx. 37.1% i HCHO) 40.5 Aqueous ammonia (approx. 28% NH:)'.'.---.. 1.5

were heated together under reflux at boiling temperature for 15 minutes. The resulting syrupy Y condensation product was dehydrated by heating it on a hotplate. The dehydrated syrupy resin was soluble in ethyl alcohol, benzyl alcohol, dioxane, ethylene glycol, -Cellosolve and var-' ious other organic solvents. A sample of the dehydrated syrup was applied to a glass plate and the coated plate then was'baked for several hours at 70 C. A hard, transparent, water-white, water-resistant, smooth and tightly adherent film was-formed onthe plate. The resinous material 01 thi example is particularly suitable for use in th e production of liquid coating com- Example 8 Parts 4,6-diamino pyrimidyl-z para-carboethoxyphenyl-carbamyl-methyl sulfide 17.4 Acrolein 28.0 Aqueous solution of sodium hydroxide (0.5

N) I 1.0 Water 20.0

The above ingredients were mixed, adding the acroleinlast, and the mixture then was heated under reflux at boiling temperature for minutes. When a sample of the resulting resinous material wa heated on a 140 C. hotplate it set to a semi-infusible state. During the period just prior to setting, the resin could be drawn into the form of fibers several inches in length. Although these fibers became brittle upon cooling to room temperature, their formation indicates that the resinous material of this example might be used a a modifier of various fiber-forming resins. The addition of chlorcacetamide, phthalic monoamide, glycine, aminoacetamide hydrochloride and other curing agents such as mentioned under Example 2, followed by heating on a 140 C. hotplate, caused the resin to convert to an infusible state. The resinous product of this example is suitable -for use in variou coating, impregnating and molding compositions. The properties of the resin indicate that it would be par-= ticularly useful as a modifier oi molding compositions where strength and toughness in the molded article are desired.

having properties very similar to the product of the previous example.

Example 9 Parts 4,6-diamino pyrimidyl-2 para-carboethoxyphenyl-carbamyl-methyl ulfide 17.4 Acetamide 3.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 81.0 Aqueous ammonia (approx. 28% NE) 1.0

Aqueous solution of sodium hydroxide (0.5

were heated together under reflux at boiling temperature for 11 minutes, yielding a resinous syrup that was clear while hot but which clouded upon cooling to room temperature. A sample of the syrupy condensation product was placed on a 140 C. hotplate and was stroked with a spatula.

The resin cured to a semi-infusible state. The

addition 01', glycine, phthalic monoamide, polysalicylide and other curing agents such as mentioned under Example 2 were not eflective in curing the resin to a completely infusible state. The resinous material of this example may be used as a modifier of other synthetic resins. For instance, it may be used as a modifier of rapidly curing aminoplasts to control their flow or plasticity charactert cs. It also may be used in coating compositronsto provide materials of better flow properties.

Example 10- Parts 4,6-diamino 'pyrimidyl-2 para-carboethoxyphenyl-carbamyl-methyl sulfide 17.4 Diethyl r'nalonate 8.0 Aqueou formaldehyde (approx. 37.1%

. Hone) 81.0 Aqueous ammonia (approx. 28% NE)..." 1.0 Aqueous solution of sodium hydroxide (0.5 1 o were heated together under reflux at boiling tem- Aqueous solution of sodium hydroxide (0.5)

were heated together under reflux at boiling temfor example hydrochloric acid, are incorporated into the dehydrated syrup prior to coating the plate with the same. The resin of this'example is particularly suitable for use as a plasticizer in molding compounds and coating compositions where products of improved flow characteristics are desired. For example, it may be used as a modifier of varnishes of the aminoplast and alkyd-resin types.

Example 12 Parts 4,6-diamino pyrimidyl-2 para-carboethoxyphenyl-carbamyl-methyl sulfide 17.4 Polyvinyl alcoho 2.2 Aqueous formaldehyde (approx. 37.1% I HCHO) 81.0 Aqueous ammonia (approx. 28% NHa) 1.0 Aqueous solution of sodium hydroxide (0.5

N) 1.0 Water 20.0

to glass plates and the coated plates then were baked for several hours at C. In all cases the baked films were hard, transparent, waterwhite, water-resistant and smooth. The films adhered tightly to the glass plates. The resinous material of this example may be used in the preparation of various molding and coating compositions.

It will be understood. of course, by those skilled in the art that the reaction between the aidehyde and the diazine derivative may be effected at temperatures ranging, for example, from room temperature tothe fusion or boiling temperatures oi the mixed reactants or of solutions of the mixed reactants, the reaction proceeding more slowly at normal temperatures than at elevated temperatures in accordance with the genperature for 5 minutes, yielding a resinous syrup 7o eral law of chemical reactions. Thus, instead of eifecting reaction between the ingredients of Examples 2 to 12, inclusive, at boiling temperature under reflux, the reaction between the components may be carried out at lower temperatures, for example at temperatures ranging from room temperature to a temperature near the boiling temperature using longer reaction periods pyrimidyl-2 .para-carboethoxyphenyl-carbamylmethyl sulfide, I may vusethe corresponding ortho or meta derivatives, the 2,6-diamino pyrimidyl-i (2,4-diamino pyrimidyl-6) ortho-, metaor paracarboethoxyphenyl-carbamyl-methyl sulfides, the diamino pyrimidyl carboalkoxytolyl-carbamylmethyl sulfides, the diamino pyrimidyl carboaryloxycarbocyclic (e. g., carbophenoxyphenyl) carbamyl-methyl sulfides, the diamino pyrimidyl carboxycarbocyclic (e. g., carboxyphenyl) carbamyl-methyl sulfides, or any other organic sulfide (or mixture thereof) of the kind with which this invention is concerned, numerous examples vof which compounds have been given hereinbefore 3nd in my copending application Serial No. 428,-

In producing these new condensation products the choice of the aldehyde is dependent largely upon economic considerations and upon the particular properties desired in the finished product. I prefer to use asthe aldehydic reactant formaldehyde or compounds engendering formaldehyde, e. g., paraformaldehyde, hexamethylene these reactants are employed in an amount corresponding to at least one mol of the aldehyde, specifically formaldehyde, for each mol of the diazine derivative. When the aldehyde is availrivative, more particularly a methylol derivative such, for instance,as dimethylol urea, trimethylol melamine, etc., then higher amounts of such aldehyde-addition products are used, for instance,

10 from 2 or 3 up to or or more mols of such alkylol derivatives for each mol of the diazine derivative.

As indicated hereinbefore, and as further shown by a number of the examples, the properties of the fundamental resins of this invention maybe varied widely by introducing other modifying bodies before, during or after effecting condensation between the primary components. Thus, as

' modifying agents I may use, for instance, monohydric alcohols such as ethyl, propyl, isopropyl, isobutyl, hexyl, etc., alcohols; p lyhydric alcohols such as diethylene glycol, triethylene gycol, pentaerythritol, etc.; amides such as formamide, stearamide, acrylamide, benzamide, toluene sulfonamides, benzene sulfonamidea'adipic diamide, phthalamide, etc.; amines such as ethylene diamine, phenylene diamine, etc.; ketones, including halogenated ketones; nitriles, including halogenated nitriles, e. g., acrylonitrile, methacrylonitrile, succinonitrile, chloroacetonitriles, etc.;

,acylated ureas, more particularly halogenated acylated ureas of the kind described, for example, in my copending applications Serial No. 289,- 273, filed August 9, 1939, now Patent No. 2,281,559,

issued May 5, 1942, and Serial No. 400,649, filed July 1, 1941, now Patent No. 2,294,873, issue September 1, 1942; and others.

The modifying bodies also may take the form of high molecular weight bodies with or without tetramine, etc. illustrative examples of other al- 40 resinous characteristics, for exampl hydrolyzed dehydes that may be employed are acetaldehyde,

propionaldehyde, butyraldehyde, methacrolein crotonaldehyde, benzaldehyde, furrural, hydroxyaldehydes (e. g., glycollic aldehyde, glyceraldehyde, etc.), mixtures thereof, or mixtures of formaldehyde (or compounds engendering formaldehyde) with such aldehydes. Illustrative examples of aldehyde-addition products that may be used instead of thefaldehydes, themselve are the mcnoand poly-(N-carbinol) derivatives, more particularly the monoand poly-methylol derivatives of urea, thiourea, selenourea and iminourea, and of substituted ureas, selenoureas, thioureas and iminoureas (numerous examples of which are given in my copending application Serial No. 377,524), monoand poly-(N-carbinol) derivatives of amides of polycarboxylic acids, e. g., maleic, itaconic, iumaric, adipic, malonic, succinic, citric, phthalic, etc., monoand poly-(N- carbinol) derivatives. of the aminotriazines, etc. Particularly good results are obtained with active methylene-containing'bodies such as a methylol urea, more particularly monoand di-methylol ureas, and a methylol melamine, e. g., monomethylol melamine and polymethyloi melamines (di-, tri-, tetra-, pentaand hexa-methylol melamines) Mixtures of aldehydes and'aldehydeaddition products may be employed, e. g., mixtures of formaldehyde and methylol compounds such, for instance, as dimethylol urea, trimethylol melamine, hexamethylol melamine, etc.

The ratio of the aldehydic reactant to the diazine derivative may be varied over a wide range depending, for example, upon the particular properties desired in the finalproduct. Ordinarilywood products, formalized cellulose derivatives, lignin, protein-aldehyde condensation products, aminotriazine-aldehyde condensation products, aminotriazole-aldehyde condensation products,

. etc. Other examples of modifying bodies are the ureaaldehyde condensation products, the anilinealdehyde condensation products, furfural condensation products, phenol-aldehyde condensation products, modified or unmodified, saturated or 5 unsaturated poiyhydrlc alcohol polycarboxylic acid condensation products, water-soluble cellu- Jose derivatives, natural gums and resins such as shellac, rosin, etc.; polyvinyl compounds such as polyvinyl esters, e. 8-. p lyvinyl acetate, polyvinyl butyrate, etc., polyvinyl others, including polyvinyl acetals, specifically polyvinyl formal, etc.

Dyes, pigments, plasticizers, mold lubricants, opacifiers, curing agents and various fillers (e. g., wood flour, glass fibers, asbestos, including. defibrated asbestos, mineral wool, mica, cloth cuttings, etc.) may be compounded with the resin in accordance with conventional practice to provide various thermoplastic and thermosetting moldingcompositions. a r

The modified or unmodified resinous compositions of this invention have a wide variety of uses. For example, in addition to their use in the f production of molding compositions, they may be usedas modifiers of other naturaland synthetic resins, as laminating in the production-of laminated articleswherein sheet materials, e. g., paper, cloth, sheet asbestos, etc., are coated and impregnated wlththe resin, su-

perimposed and thereafter united under heat and' pressure. They may be employed inthe producable for reaction in the form of an alkylol de of electrical resistors, etc.

' asreyos tion of wire or baking'enamels from which insulated wires and other coated products are made, for bonding or cementing together mica flakes to form a laminated mica article, for bonding together abrasive grains in the production of resinbonded abrasive articles such, for instance, as

grindstones, sandpapers, etc., in the manufacture They also may be employed for treating cotton, linen and other cellulosic materials in sheet or other form. They also may be used as impregnants for electrical coils and for other electrically insulating applications.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. A composition of matter comprising the re-= action product of ingredients comprising an aldehyde and a compound corresponding.to the general formula (RENT 1 j \N where n represents an integer and is atleast 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, Y rep- 4. A composition comprising the condensation product of a plurality of reactants including an 40 curing reactant is a ch mated Meta m1 de.

1'7. A composition comprising the product of aldehyde and a compound corresponding to the general formula where Y represents a divalent carbocyclic radical,

' p and R represents a member of the class consisting of hydrogen andmonovalent hydrocarbon and-'halo-hydrocarbon radicals.

5. A composition comprising thecondensation productof ingredients comprising an aldehyde and a diamino pyrimiidyl carboaliphaticoxyoarbocyclic-carbamyl-methyl sulfide.

6. A composition comprising the condensation product of ingredients comprising an aldehyde dehyde and a diamino pyrimidyl carboallroxyaryh canbamyl-methyl sulfide.

(mm in i C C J product or reaction: of ingredients comprising an aldehyde and a diamino pyrimidyl canboethoxy- V phenyl-carbamyl methyl sulfide.

11. A resinous composition comprising the product of reaction of a mixture containing formaldehyde and 4,6-diamino pyrimidyl-Z paracarboethoxyphenyl-carbamyl-methyl sulfide.

12. A composition containing as an essential component the product of reaction of ingredients 10 comprising an aldehyde and a diamino pyrimidyl carboalkoxytolyl-carbamyl-methyl sulfide.

13. A composition comprising the product of reaction of ingredients comprising a urea, an aldehyde and a compound corresponding to the 15 general formula V v where n represents an integer and is at least 1 and not more than 2 2- represents a. member of the class consisting of oxygen and sulfur, Y represents a divalent carbocyclic radical, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-by drocarbon radicals.

14'. A composition as in claim 13 wherein the urea component is the compound corresponding to the formula NHzCONH: and the aldehyde is formaldehyde.

15. A heat-curable composition comprising the heat-convertible resinous reaction product of (l) a partial condensation product of ingredients comprisi'ng'formaldehyde and diamino pyrimidyi carboalkoxycarbocyclic c rbamyl methyl sulfide. and (2) a curing reactant.

16. A composition as in claim 15 wherein the reaction of ingredients comprising urea, formaldehyde sliid a diamino pyrimidyl carboxyarylcarbamyl-methyl sulfide.

d8 18. A composition containing the resinous product or reaction of ingredients comprising a -methylol urea and a diamino pyrimidyl carboalkomryl-carbamyl-methyl sulfide.

19. .A composition comprising the condensation product of a plurality of reactants includin melamine, formaldehyde and a diamino pyrimidyl carboalkoxyaryl-carbamyl-methyl sulfide.

20.,The method of preparing new condenser,

' tion products which comprises efiecting reaction where n represents an integer and is at least 1 8. A heat-curable resinous composition 00m? 05 and t more than 2, 2 represents a member prising a'heat-convertible condensation product of ingredients comprising formaldehyde and a diamino pyrimidyl carboslkoxyphenyl-carbamylmethyl sulfide.

of the class consisting, of ongen and sulfur,

Y represents a divalent carbocyclic radical, and It represents a member of the class consisting of hydrogen and monovalent hydrocarbon and .7 halo-hydrocarbon radicals.

ammo r. DALEH 

